It is still unclear how the aid will get through the Colombian-Venezuelan border.
He accused the Trump administration of trying to violate national sovereignty by co-ordinating the shipment of hundreds of tonnes of medicines, medical equipment and nutritional supplements.
Speaking in its inaugural meeting in the Uruguayan capital of Montevideo, the EU-backed International Contact Group on Venezuela said overly forceful intervention could aggravate the crisis in the country.
Venezuelan volunteers place a bag of USAID humanitarian aid for storage at a warehouse next to the Tienditas International Bridge, near Cucuta, Colombia, on the border with Venezuela, Friday, Feb. 8, 2019.
Guadio is backed as the de facto leader by more than 40 nations, including the USA and major European powers, who want Maduro to step down.
"Venezuela isn't going to allow a false show of humanitarian aid, because we're not beggars".
"We reject the partisan and ideological nature of the document", Maduro said on Friday, adding that he would always welcome dialog with anyone.
Maduro also repudiated a statement issued by the International Contact Group on Venezuela.
Last week Reuters reported that senior United States government officials are in direct talks with the country's military to convince them to back Guaido, who has offered soldiers amnesty to work against the Maduro government.
China, Iran, Russia and Turkey have put their weight behind Maduro.
The US, Canada and some other countries recognised him nearly immediately, while the UK, Germany, France, and Spain later declared their intention to recognise Guaido if Caracas did not announce snap presidential elections within eight days.More news: Migrant caravan reaches town on Texas border
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Venezuela is in the midst of a power struggle following the National Assembly's declaration that Maduro is an usurper, and several countries - including the USA - now recognize opposition leader Juan Guaido as the nation's legitimate president.
A Senior White House official has revealed that the United States is actively in direct talks with the military in Venezuela urging them to abandon headstrong leader Nicolas Maduro.
"The main objective here is to bring humanitarian assistance - and if it must be done by military support, so be it", he said at a news conference at United Nations headquarters in NY.
"I'm sure that Moscow as much as Beijing is very aware of the situation in Venezuela, that Maduro doesn't have popular support, the he can't stabilise the economy. all the while holding the biggest oil reserves in the world".
The opposition leader and self-declared Interim President Juan Guaidó has said Venezuelans will die without it.
Last month, the 35-year-old Guaido was named leader of the opposition-controlled National Assembly.
Leftist-led Bolivia also refused to support snap presidential elections in Venezuela. "You're deaf... They've taken extremist positions".
They want to invade and intervene in Venezuela - they say, as they said then - in the name of democracy and freedom.
Medina previously served as a legal adviser at Venezuela's U.N. Mission.
Guaido agrees that no-one will come to Maduro's rescue.